Foaming hair coloring compositions comprising basic dyes, and method of use



United States Patent C) FOAMING HAIR COLORING COMPOSITIONS COMPRISINGBASIC DYES, AND METHOD OF USE Marion Den Beste, Prospect Heights, Ill.,asfsignor to Rayette, Inc., a corporation of Minnesota No Drawing.Application February 1, 1952, Serial No. 269,600

4 Claims. (Cl. 132--7) The present invention relates to cosmeticcompositions and has particular reference to cosmetic compositionsadapted for imparting color to human hair.

From earliest history many people have been dissatisfiied with thenatural color of their hair and have sought preparations capable ofmodifying its color. Numerous color modifying materials and many variedprocedures for applying such materials to human hair have been dv'veloped in an attempt to formulate a hair coloring cosmetic preparationsuitable for convenient home use by the consumer.

The hair coloring compositions which have been suggested heretofore havecertain disadvantages which limit the desirability for their use. Aprimary disadvantage inherent in prior art preparations is that thecolor imparted through the use of such preparations is absorbedpermanently by the hair. Should the user become dissatisfied with thecolor there may be nothing that can be done to remove the same except todye the hair with another color to cover the undesirable shade obtainedin the first application.

The dyes or the dye intermediates used in prior art compositions arepermanently affixed to the hair through the conjoint use of auxiliaryagents, e. g., oxidizing agents, dye precipitating agents or mordantingagents. The application of such auxiliary agents to afiix a dye andthereby develop color on hair is undesirable because such agents alsoattack and embrittle the hair. In addition to permanently affixing thedye on the hair the use of such agents is also objectionable since manysuch auxiliary agents are toxic and irritating to the skin.

For many years dye chemists and cosmetic manufacturers have been awareof the above described disadvantages inherent in prior art hair coloringcompositions. So far as is known, However, all previous attempts toformulate a preparation for coloring human hair lacking or substantiallyminimizing the above described disadvantages have been unsuccessful.

The surprising discovery has now been made that novel hair coloringcompositions can be prepared which do not possess the disadvantages andlimitations of the hair coloring compositions heretofore known. Thenovel compositions of the present invention comprise foaming haircoloring cosmetic compositions comprising a hair coloring component inadmixture with a foaming surface active material.

The hair coloring component comprises at least one non-irritating,non-sensitizing basic dye which is capable of being selectively adsorbedfrom a solution of the composition by the hair. i

The surface active material employed in these novel compositionscomprises foaming surface active agents selected from the groupconsisting of non-ionic surface active agents and surface active agentsobtained by condensing protein degradation products with fatty acylhalides, such being so weakly anionic as to be substantially non-ionic.I

Accor'ding to the present invention the surprising dis- 2,763,269Patented Sept. 18, 1956 covery has been made that a basic dye suspendedin a solution of a foaming surface active agent of the type hereindescribed provides a new and markedly improved composition for coloringhuman hair. Basic dyes have been found to be suitable for coloring humanhair since such dyes are amenable to selective adsorption by the hairfrom solutions containing the particular type of foaming surface activeagents herein described. I

An outstanding feature of the combination of the particular dyes and thesurface active agents of this inven-' tion is that the said basic dyesare deposited on the hair in the presence of the particular non-ionicand substantially non-ionic surface active agents herein described andare readily removable therefrom upon subsequent shampooing with ananionic sulfate or sulfona-te type shampoo, e. g., the ammonium salt ofthe mono-sulfated monoglyceride of coconut oil fatty acids which is morestrong ly ionizable than the substantially non-ionic surface activeagents herein described.

A further outstanding characteristic of this combination is that theparticular dyes may be applied from a foam for optimum distribution fora level coloring or tinting of the hair from a desirably small quantityof fluid. Thus, about two tablespoonsful of the composition aresufficient for level tinting of the whole head of hair as a result ofits conversion into a large mass of foam at the time of use.

As indicated hereinbefore the dyes which may be used in the novelcompositions of the present invention are non-irritating andnon-sensitizing to the skin. A dye which is irritating to the skin, i.e., a cutaneous irritant, is one which will cause dermatitis by directaction on the normal skin at the site of contact. A dye which issensitizing to the skin, i. e., a cutaneous seusitizer, is one whichdoes not necessarily cause demonstrable cutaneous changes on firstcontact but one which may eifect such specific changes in the skin that,after 5 to 7 days or more, further contact on the same or other parts ofthe body will cause dermatitis.

Irritation and sensitization determinations of basic dyes may be made inany convenient manner. According to one method a fii-inch square pieceof 4-ply gauze is saturated with the dye and applied to uninflamed skinbehind the ear. This is sealed to the skin with adhesive plaster. Thegauze or patc is left in place for 24 hours. The reaction-s are readimmediately upon removal of the patch and for several days thereafter.Dyes which give negative reaction-s after two patch tests 5 to 7 daysapart are both non-irritating and non-sensitizing to the skin and aresuitable for use in accordance with this invention.

Representative examples of water soluble basic dyes which arenon-irritating and non-sensitizing include:

By blending various dyes, it is possible to produce a complete range ofshades which appear natural in color and which are non-injurious to thehair and scalp. The invention is not limited to the use of theparticular dyes mentioned, inasmuch as any of the great number of otherdyes possessing the definitive characteristics set forth hereinabove maybe employed.

It is essential that the surface active materials used in formulatingthe novel compositions of the present invention be capable of formingrelatively large amounts of foam. The foam apparently acts as a vehicleor a carrier for the dye and assures a thorough and uniform distributionof the same upon the individual hair filaments.

Representative examples of suitable non-ionic surface active materialswhich may be employed in the present invention include those compoundsderived from the reaction of fatty acids and alcohols having about 12 to30 carbon atoms per molecule with sufiicient ethylene oxide groups toform surface active materials having the desired foaming propertiesdescribed, e. g., polyethylene glycol oleate, polyethylene glycol etherof lauryl alcohol, etc.; the high molecular weight derivatives ofpolyhydroxy compounds such as polyalkylene glycols and polyglycerols, e.g., alkyl thio-ethers of polyethylene glycol (stearyl thio-ether ofpolyethylene glycol), sterol ethers of polyethylene glycol (cholesterolether of polyethylene glycol), alkyl phenol ethers of polyethyleneglycol having an average of about 8.5 to oxyethylene groups (n- Nonylphenyl ether of polyethylene glycol); the corresponding derivatives ofpolypropylene glycol, polybutylene glycol, and polyglycerol;polyalkylene glycol ethers of partially esterified glycerol(polyethylene glycol ether of monostearin), sorbitol (polyethyleneglycol ether of sorbitol oleate), sorbitan (sorbitan monostearatepolyoxyethylene); etc.

Additional examples of surface active materials which may be employed inthis invention include surface active agents prepared by hydrolyzingwaste protein materials of high molecular weight, e. g., scrap leather,glue, or other hydrolyzable collagens, with alkali. The hydrolyzate thusobtained is a complex comprising lower polypeptides and some hydrolyticproducts thereof, e. g., free amino acids. This complex then iscondensed with a fatty acyl halide. During the condensation the aminogroups of the polypeptides and of the amino acids are converted to amidederivatives of the fatty acyl halide. The condensation product thusobtained has excellent foaming properties. This product bears aresemblance to anionic surface active agents but is so weakly ionizableas tobe substantially non-ionic in its action in admixture with thebasic dyes herein described and is suitable for use in the novelcompositions of the present invention.

The particular fatty acyl halides used in the condensation reactionsdescribed may be formed by reacting a suitable halide material witheither the mixed fatty acids obtained from tallow, coconut oil, peanutoil, soy bean oil, etc., or with any of the individual fatty acids whichmay be derived from these oils. Suitable fatty acids include thosecontaining about 8 to 24 carbon atoms and preferably those containing 12to 18 carbon atoms per molecule.

Sufficient surface active material is incorporated in the novelcompositions herein disclosed to assure the provision of a compositionhaving the satisfactory foaming characteristics described. It has beenfound that products containing about 5 to surface active material byweight of the final composition provide completely satisfactoryproducts. Although the surface active material may be present insomewhat higher concentrations, no particular advantages are obtainedthereby. Moreover, an increase in the concentration of the surfaceactive material necessarily results in an increase in the cost of thefinal composition without affording any increase in product quality.

The amount of dye which has been found to be satisfactory for use incompositions having a concentration of surface active material as setforth hereinabove falls within the range of about 0.05 to 2.5% by weightof the finished product.

The present invention, in the broadest aspects thereof, contemplatesthat the novel hair coloring compositions may be prepared and marketedin any desired physical form, e. g., in an aqueous form such as aliquid, paste, or

gel; as a dry powder; etc. When sold as a paste or gel or in a drypowder form the compositions are preferably dissolved by the user in anaqueous solvent medium, similar to that employed when manufacturing thecompositions in liquid form, prior to, application to the hair. Such amedium is requisite for the provision of a hair coloring compositionhaving satisfactory foaming properties. Water (tap water, distilledwater, deionized water, etc.) has been found to be a satisfactory mediumfor the particular surface active materials and dyes herein described.The amount of the aqueous solvent employed generally should amount to atleast about 80% and preferably about to of the total weight of thefinished composition.

In order to indicate even more fully the advantages and capabilities ofthe novel compositions of the present invention, the following specificexamples of representative hair coloring cosmetic compositions are setforth. The formulations have been set forth for illustrative purposesonly and they are not intended to limit the scope of the invention inany manner.

Example I A hair coloring cosmetic composition capable of imparting asilver color to white or grey hair comprises:

Per cent Protein condensate with oleyl chloride 8.0 Calcozine Orange RS0.04 Benzyl Violet DSC H 0.027 Basic Blue FN Ex 0.027 Safranine T Ex0.007 Sodium alginate 1.0 Perfume 0.1 Boric acid U. S. P. powder 0.960Water Balance Example II A hair coloring cosmetic composition capable ofim parting a grey color to white or grey hair comprises:

Per cent Protein condensate with oleyl chloride 8.0 Calcozine Orange RS0.120 Benzyl Violet DSC 0.080 Basic Blue FN Ex 0.080 Safranine T Ex0.020 Sodium alginate 1.0 Perfume 0.1 Boric acid U. S. P. powder 0.960Water Balance Example III A hair coloring cosmetic composition capableof imparting a black color to light or dark colored hair comprises:

Product obtained by condensing a higher fatty acid with 2 moles ofdiethanolamine.

Example IV A hair coloring cosmetic composition capable of imparting asilver color to white or grey hair comprises:

Per cent iso-Octyl phenoxy heptaethylene glycol 14.000 Calcozine OrangeRS 0.040 Benzyl Violet DSC 0.027 Basic Blue FN Ex 0.027 Safranine T F0.027 Water Balance Y Exa'mple V A hair coloring cosmetic compositioncapable of imparting a silver color to White or grey hair comprises:

. Percent n-Nony-l phenoxy nonaethylene glycol 7.600 CalooZin-e OrangeRS 0.040 Benzyl Violet DSC 0.0 Basic Blue -FN Ex 0 .016 Safranine T EX0.004 Perfume 0.050 Water Balance Example VI A hair coloring cosmeticcomposition capable of imparting a grey or a steel grey color to grey orpredomi nantly grey hair comprises:

7 Percent Polyethylene glyco tert-dodecyl thio ether 10.200 Basic BrownGXP 0.093 Cyper Black IA 0.1 16 Safranine T EX 0.046 Methylene Blue ZX0.046 Water Balance Example VII A hair coloring cosmetic compositioncapable of imparting a black color on light or dark colored hair comprises:

Percent Polyethylene glyco tert-dodecyl thio ether 8.000 Cyper Black IA0.660 Basic Brown GXP 1.000 Safr-anine T Ex 0.400 Methylene Blue ZX0.440 Water Balance Example VIII A hair coloring cosmetic compositioncapable of imparting a black color on light or dark colored haircomprises:

A hair coloring cosmetic composition capable of imparting a dark browncolor on light or dark colored hair comprises:

Percent n-Nonyl phenoxy nonaethylene glycol 5.80 Basic Brown GXP 0.75Benzyl Violet DSC 0.115 Methylene Blue ZX 0.:' Safranine T Ex 0.15 WaterBalance Exalmple X A hair coloring cosmetic composition capable of imparting a dark brown color on medium or dark brown hair comprises:

Per cent iso-Octyl phenoxy heptaethylene glycol 11.00- Basic Brown GXP1.57 Benzyl Violet DSC 0.31 Methylene Blue ZX 0.31 Sarfranine T EX 0.31Water Balance Example XI A hair coloring cosmetic composition capable ofparting reddish-brown highlights on brown or medium brown haircomprises:

Per cent n-Nonyl phenoxy decaethylene glycol 9.20 Basic Brown GXP 0.20Calcozine Orange RS 0.15 Basic Blue FN 0.05 Safranine T Ex 0.05Methylene Blue ZX 0.02 Boric acid U. S. P. powder 1.00 Perfume 0.10Water Balance Example XII A hair coloring cosmetic composition capableof imparting reddish-gold highlights to light blonde or ash blonde haircomprises:

. Per cent n-Nonyl phenoxy nonaethylene glycol 5.00 Safranine T Ex 0.01Oalcozine Orange RS 0.06 Boric acid U. S. P. powder 1.00 Perfume 0.10Water Balance Example XIII A hair coloring cosmetic composition capableof imparting auburn highlights on auburn or dark bnown hair comprises:

Percent Protein condensate with oleyl chloride 8.500 Basic Brown GXP0.625 Basic Blue EN 0.050 Benzyl Violet DSC 0.050 Safranine T Ex 0.275Sodium alginate 1.000 Perfume 0.100 Boric acid U. S. P. powder 0.960Water Balance Example XIV v A hair coloring cosmetic composition capableof imparting a brown color to light auburn, dark auburn or dark brownhair comprises:

The novel hair coloring compositions of the present invention areadapted for convenient home use by the consumer. Prior to using any oneof these compositions the hair preferably is given a thorough cleansingtreatment by washing with a good quality non-soap shampoo. Aftersubstantially all dirt, grease and the like has been removed a lustrousnew hair color may be obtained upon a single application of thecompositions herein described.

Any desired tint or color may be imparted to the hair by applyingthereto, in several small portions, the particular coloring compositionwhose color is desired. The portions are applied around the top of thehead about one-half inch from the scalp, each portion being worked intoa foam before applying the next portion. After all the portions havebeen applied the foam is worked throughout the entire head of hair toinsure even distribution. The hair is then rinsed thoroughly with waterand then toweled-dry.

By using the novel compositions of this invention color is imparted tothe hair immediately upon contact, i. e., no Waiting or setting periodis required. The compositions, When correctly applied, will not rub offon clothing or pillows. Furthermore, the color imparted, while resistantto attack by the sun, rain, etc., may be removed satisfactorily and thehair restored to its natural color upon subsequent shampooing withanionic sulfate or sulfonate type shampoo compositions. The simplicityof the process makes it obvious that no expert beauty parlor applicationis necessary.

The addition of various adjuvant materials to the novel hair coloringcompositions is contemplated by the present invention. Thus, thecompositions ordinarily will contain a perfume which should be selectedso as to be compatible with the character of the finished product. Also,ingredients which impart further desired qualities to the hair may beincorporated in the present compositions. Hair conditioners, forexample, or superfatting materials or foam boosters such as lanolin,lecithin, fatty amides, etc., generally may be used in minorproportions. Furthermore, small amounts of thickening agents such assodium alginate may be included to reduce the fluidity of the product.Moreover, suitable preservatives may be incorporated in minor amounts asneeded to prevent or substantially minimize the formation of mold.

In preparing the novel composition of the present invention in aqueousform the formula amounts of the dyes are dispersed in about 70% of thewater. The mix is heated to a temperature around 110 to 120 F. and

thoroughly agitated until all of the dye is dispersed. Should any dyeparticles remain undispersed, the same may be removed in any convenientmanner, e. g., by filtration, decantation or the like. The surfaceactive material then is introduced into the mix with moderate agitationand at a rate slow enough to prevent lumping and the incorporation ofair. Any compatible perfume and preservatives are then added.

While there has been disclosed and described What is at presentconsidered to be the preferred embodiment of the present invention, itwill be understood, of course, that many modifications and changes andsubstitutions may be made therein Without departing from the true scopeof the invention as defined in the appended claims.

Having thus described the invention, What is claimed 1. A cosmeticcomposition which in aqueous form is adapted for coloring human hairwhich comprises about 0.05% to about 2.5% of at least onenon-irritating, nonsensitizing water soluble basic dye capable of beingselectively adsorbed from an aqueous solution of the composition byhair, about 5% to about 15% of a foaming surface active material, saidfoaming surface active material being selected from the group consistingof nonionic surface active agents and substantially non-ionic surfaceactive agents obtained by condensing protein degradation products withfatty acyl halides.

2. A foaming hair coloring composition in liquid form comprising incombination about 0.05 to about 2.5 of at least one non-irritating,non-sensitizing water soluble basic dye capable of being selectivelyadsorbed from a solution of the composition by hair, about 5% to about15% of a foaming surface active material, a major proportion of anaqueous solvent medium, and small but effective amounts of apreservative and a thickener, said foaming surface active material beingselected from the group consisting of non-ionic surface active agentsand substantially non-ionicsurface active agents obtained by condensingprotein degradation products with fatty acyl halides.

3. A process for coloring hair which comprises shampooing the hair witha strongly ionizable anionic surface active agent, rinsing the hair withwater to remove said anionic surface active agent, applying to the haira foaming hair coloring composition which comprises about 0.05% to 2.5%of at least one non-irritating, non-sensitizing, water soluble basic dyeand about 5 to 15 of foaming surface active material selected from thegroup consisting of non-ionic surface active agents and substantiallynon-ionic surface active agents obtained by condensing proteindegradation products with fatty acyl halides, working said coloringcomposition throughout the hair, and thereafter rinsing the hair withwater.

4. A non-irritating, non-sensitizing, cosmetic composition adapted forcoloring human hair comprising an aqueous medium having dissolvedtherein about 0.5% to about 2.5% of at least one water soluble basic dyeand about 5% to about 15% of a foaming surface active material selectedfrom the group consisting of non-ionic surface active agents andsubstantially non-ionic surface active agents obtained by condensingprotein degradation products with fatty acyl halides, said basic dyebeing capable of being selectively adsorbed by hair from said aqueousmedium.

References Cited in the file of this patent UNITED STATES PATENTS1,930,853 Kollek Oct. 17, 1933 1,970,578 Schoeller Aug. 21, 19342,015,912 Sommer Oct. 1, 1935 2,100,090 Sommer Nov. 23, 1937 2,151,241Sommer a- Mar. 21, 1939 2,208,594 Orelup July 23, 1940 2,643,211 DenBeste June 23, 1953 2,695,259 Charle Nov. 23, 1954 FOREIGN PATENTS240,909 Switzerland May 16, 1946 197,425 Switzerland Aug. 1, 1938307,944 Great Britain Mar. 11, 1929 531,153 Germany Aug. 6, 1931 397,219Germany June 17, 1924 OTHER REFERENCES Janistyn: Riechstofie, Seifen,Kosmetika, Alfred Huthig Verlag, Heidelberg, 1950, vol. 2, pp. 455 and456, especially F. Shampoo mit Haarfarben.

Redgrove: Hair-Dyes and Hair-Dyeing," Chemical Publishing Co., N. Y.,1939, p. 104.

Bennett: Cosmetic Formulary, Chemical Publishing Co., N. Y., 1937, p.127.

1. A COSMETIC COMPOSITION WHICH IN AQUEOUS FORM IS ADAPTED FOR COLORINGHUMAN HAIR WHICH COMPRISES ABOUT 0.05% TO ABOUT 2.5% OF AT LEAST ONENON-IRRITATING, NONSENSITIZING WATER SOLUBLE BASIC DYE CAPABLE OF BEINGSELECTIVELY ADSORBED FROM AN AQUEOUS SOLUTION OF THE COMPOSITION BYHAIR, ABOUT 5% TO ABOUT 15% OF A FOAMING SURFACE ACTIVE MATERIAL, SAIDFOAMING SURFACE ACTIVE MATERIAL BEING SELECTED FROM THE GROUP CONSISTINGOF NONIONIC SURFACE ACTIVE AGENTS AND SUBSTANTIALLY NON-IONIC SURFACEACTIVE AGENTS OBTAINED BY CONDENSING PROTEIN DEGRADATION PRODUCTS WITHFATTY ACYL HALIDES.